CN102095812B - Method for detecting acrylonitrile in cosmetics by using gas chromatograph-mass spectrography - Google Patents
Method for detecting acrylonitrile in cosmetics by using gas chromatograph-mass spectrography Download PDFInfo
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- CN102095812B CN102095812B CN 201010559761 CN201010559761A CN102095812B CN 102095812 B CN102095812 B CN 102095812B CN 201010559761 CN201010559761 CN 201010559761 CN 201010559761 A CN201010559761 A CN 201010559761A CN 102095812 B CN102095812 B CN 102095812B
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Abstract
The invention discloses a method for detecting acrylonitrile in cosmetics by using the gas chromatograph-mass spectrography, which comprises the followings steps of: adding methanol in a sample to be measured, ultrasonically extracting, centrifuging an extract, taking the supernate, drying the supernate with nitrogen, dissolving the dried supernate with a 10-percent methanol aqueous solution, purifying with a hydrophilic and lipophilic solid-phase extraction column, eluting the hydrophilic and lipophilic solid-phase extraction column with methanol aqueous solution of 80-percent volume percent, dehydrating the obtained eluent, concentrating, filtering the eluent with a filter membrane, and carrying out gas chromatogram-mass spectrum measurement, wherein the chromatographic column of the gas chromatogram is of bonding/cross-linked polyglycolic stationary-phase, the specification is 60m*0.25mm*0.50Mum, the temperature of the chromatographic column is increased in a programmed way, is maintained at 60 DEG C for 3 minutes, then increased to 100 DEG C by the increase rate of 4 DEG C/min and maintained at 100 DEG C for 2 minutes, and increased to 220 DEG C by the increase rate of 20 DEG C/min, the samples are fed in a split way, and the split ratio is 10 to 1. The method for detecting acrylonitrile in cosmetics by using the gas chromatograph-mass spectrography is fast, and has low detection limit and high recovery rate.
Description
Technical field
The present invention relates to the method for the vinyl cyanide in a kind of Cosmetics by Gas Chromatography-Mass Spectrometry.
Background technology
Along with improving constantly of the flourish and living standards of the people of Chinese national economy, cosmetics have become the important consumer goods of people's daily life, and the security of cosmetics also is subject to the public's extensive concern day by day.Antiseptic is the important source material of cosmetics, the many manufacturer production of recent year the Special Antiseptics for Cosmetics of numerous kinds, but contain vinyl cyanide because the antiseptic improper use makes the cosmetics finished product.In addition, also may residual acrylonitrile monemer in the toiletry bag package material, due to storage or the improper use of cosmetics, its directly container of contact contain or discharge vinyl cyanide.Have a strong impact on the safety of cosmetics, the consumer health is threatened.China's cosmetics health standard and European Union's cosmetics rules (Cosmetic Regulation EC1223/2009) all clear vinyl cyanide are the components of cosmetics banned substance.
Because the vinyl cyanide boiling point is low, poor chemical stability, domestic and international mensuration for vinyl cyanide adopts headspace gas chromatography and hot analytical method more at present.Headspace gas chromatography is with fastest developing speed, one of most widely used method for separating and analyzing, it is also the Main Analysis method of measuring vinyl cyanide, both at home and abroad it being measured in association areas such as food, aquatic products has more report, and at cosmetic field, so far for extremely, mensuration to vinyl cyanide remains blank, matrix mainly due to cosmetics is complicated, the form variation, and this has increased the difficulty of head space method test.
Summary of the invention
The purpose of this invention is to provide that a kind of detectability is low, the recovery is high, the method for the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry fast.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry provided by the present invention comprises the steps:
Add methyl alcohol in testing sample, ultrasonic extraction, extract is centrifugal, gets supernatant, nitrogen dries up, then 10% methanol aqueous solution dissolving uses hydrophilic lipophilic Solid-Phase Extraction column purification, the percent by volume 80% hydrophilic lipophilic solid-phase extraction column of methanol aqueous solution wash-out, the eluent that obtains dewaters, concentrated, membrane filtration carries out Gas Chromatography-Mass Spectrometry;
The chromatographic column of gas chromatography is the fixedly chromatographic column of phase of bonding/crosslinked PVOH, and specification is 60m * 0.25mm * 0.50 μ m;
The chromatographic column adopting temperature programme: 60 ℃ keep 3min, and then 4 ℃/min is warming up to 100 ℃ of maintenance 2min, then is warming up to 220 ℃ with 20 ℃/min;
Split sampling, split ratio are 10: 1.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention, wherein said cosmetics are cream frost, aqua, loose powder or shampoo.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention, wherein said cosmetics are lipstick, add tetrahydrofuran before the ultrasonic extraction of described testing sample.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention adds 40mL methyl alcohol in wherein said 1g testing sample.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention adds 40mL methyl alcohol and 1mL tetrahydrofuran in wherein said 1g testing sample.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention, wherein said ultrasonic extraction time is 20min.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention, wherein said centrifugal rotational speed 10000r/min, centrifuging 15min.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention detects and is limited to 4mg/kg, and the recovery is between 84.0%～101.0%, and relative standard deviation is between 1.1%～4.2%.
Description of drawings
Fig. 1 is that HP-Innowax (30m * 0.25mm * 0.25 μ m) is to the separating spectrum of vinyl cyanide.
Fig. 2 is that HP-Innowax (60m * 0.25mm * 0.50 μ m) is to the separating spectrum of vinyl cyanide.
Embodiment
Agilent 6890-5975 gas chromatograph-mass spectrometer (GCMS) is furnished with electron impact ionization source (U.S. Aglient company);
Oasis HLB solid-phase extraction column, (6mL, 200mg, U.S. Waters company);
Methyl alcohol, tetrahydrofuran (chromatographically pure, U.S. Fisher company), vinyl cyanide standard substance (purity 〉=97%) is available from German Dr.Ehrenstorfer company.
Standard reserving solution: accurately take 0.100g (being accurate to 0.001g) vinyl cyanide, use methanol constant volume 100mL, shake up.Be mixed with 1000 μ g/mL vinyl cyanide standard reserving solutions, preserve under-20 ℃.
Standard operation liquid: with methyl alcohol, standard reserving solution is diluted to respectively the standard operation liquid of 0.1,0.2,0.5,1.0 and 2.0 μ g/mL, standby.
The processing of cream frost, aqua, loose powder, shampoo class sample: accurately take three parts of cosmetics sample 0.5g and be placed in 50mL tool plug conical flask, add respectively 20mL methyl alcohol, ethanol and methylene chloride, put ultrasonic extraction 20min in ultrasonic extractor, said extracted liquid is poured in centrifuge tube with 10000r/min centrifuging 15min, got supernatant, adopt 35 ℃ of nitrogen to blow near and do, be settled to 1mL with 10% methanol aqueous solution, with commodity post C
18Post (Sep-Pak C
18), silicagel column (Sep-Pak Silica), hydrophilic lipophilic post (Oasis HLB) purify said extracted liquid respectively.Adopt the pre-drip washing of 5mL methyl alcohol, the 5mL water balance with 1mL sample loading after above processing, first with 1mL 20% methanol-water drip washing, discards leacheate, then with 3mL 80% methanol-water wash-out, collects eluent.Through anhydrous sodium sulfate dehydration, 35 ℃ of nitrogen blow and are concentrated into 1mL, and through membrane filtration, gas chromatography-mass spectrum carries out qualitative and quantitative analysis.
The processing of lipstick class sample: accurately take three parts of cosmetics sample 0.5g and be placed in 50mL tool plug conical flask, add respectively 20mL methyl alcohol, ethanol and methylene chloride, add again the 0.5mL tetrahydrofuran, put ultrasonic extraction 20min in ultrasonic extractor, said extracted liquid is poured in centrifuge tube with 10000r/min centrifuging 15min, get supernatant, adopt 35 ℃ of nitrogen to blow near and do, be settled to 1mL with 10% methanol aqueous solution, with commodity post C
18Post (Sep-Pak C
18), silicagel column (Sep-Pak Silica), hydrophilic lipophilic post (Oasis HLB) purify said extracted liquid respectively.Adopt the pre-drip washing of 5mL methyl alcohol, the 5mL water balance with 1mL sample loading after above processing, first with 1mL 20% methanol-water drip washing, discards leacheate, then with 3mL 80% methanol-water wash-out, collects eluent.Through anhydrous sodium sulfate dehydration, 35 ℃ of nitrogen blow and are concentrated into 1mL, and through membrane filtration, gas chromatography-mass spectrum carries out qualitative and quantitative analysis.
Chromatographic condition:
Chromatographic column: HP-Innowax (30m * 0.25mm * 0.25 μ m); HP-Innowax (60m * 0.25mm * 0.50 μ m);
Injector temperature: 200 ℃;
Flow rate of carrier gas: 1.2mL/min (constant current mode), split sampling, split ratio 10: 1;
Temperature programme: 60 ℃ of initial temperatures (keeping 3min) are warming up to 100 ℃ (keeping 2min) with 4 ℃/min, then are warming up to 220 ℃ with 20 ℃/min; Bulk analysis time 21min.
The mass spectrum condition:
Chromatography-mass spectroscopy interface temperature: 250 ℃;
Ion source temperature: 230 ℃;
Ionization mode: EI, the mass scanning scope is (10～100) amu;
Solvent delay: 5min;
Monitoring mode: select ion monitoring (SIM);
Selecting qualitative ion is 53,52,26, and wherein quota ion is 53.
Experimental result shows, when ethanol is done when extracting solution, and the appearance time phase mutual interference of ethanol and test substance; When methylene chloride was made the extraction solvent, methylene chloride was relatively poor to the dissolubility of cosmetics, and has not dissolution phenomena with lipstick; When adopting methyl alcohol to make the extraction solvent, the methyl alcohol extraction recovery is higher, and chromatographic peak disturbs few.The organic efficiency of Oasis HLB post is best, and the eluting solvent consumption is little.Oasis HLB solid phase extraction column is that the macroporous copolymer that aggregates into by a certain percentage with lipophilicity divinylbenzene and two kinds of monomers of water wettability NVP is as the reverse phase solid phase extraction pillar of filler, can effectively remove the Various Complex matrix in cosmetics, few as the impurity of eluting solvent wash-out with 80% methanol-water solution, the recovery to target compound is the highest, only use the target compound that 3mL can the wash-out higher amount, purify the sample used time short.When selecting polar solvent, in HP-Innowax (30m * 0.25mm * 0.25 μ m) post, the situation that exists vinyl cyanide to separate with the solvent peak difficulty, as shown in Figure 1, wherein 1 is vinyl cyanide, 7.8min the peak be impurity, find that vinyl cyanide at the place, end of solvent peak, is difficult to reach fully with solvent separate.HP-Innowax (60m * 0.25mm * 0.50 μ m) post, because its post is longer, fixedly the phase liquid film is relatively thicker, and is more abundant complete to separating.Fig. 2 be HP-Innowax (60m * 0.25mm * 0.50 μ m) to the separation graph of vinyl cyanide, wherein 1 is vinyl cyanide.
In sum, the method for the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention is as follows:
The processing of cream frost, aqua, loose powder, shampoo class sample: accurately take cosmetics sample 0.5g and be placed in 50mL tool plug conical flask, add 20mL methyl alcohol, put ultrasonic extraction 20min in ultrasonic extractor, said extracted liquid is poured in centrifuge tube with 10000r/min centrifuging 15min, get supernatant, adopt 35 ℃ of nitrogen to blow near and do, be settled to 1mL with 10% methanol aqueous solution, with Oasis HLB solid-phase extraction column, said extracted liquid is purified.Adopt the pre-drip washing of 5mL methyl alcohol, the 5mL water balance with 1mL sample loading after above processing, first with 1mL 20% methanol-water drip washing, discards leacheate, then with 3mL 80% methanol-water wash-out, collects eluent.Through anhydrous sodium sulfate dehydration, 35 ℃ of nitrogen blow and are concentrated into 1mL, and through membrane filtration, gas chromatography-mass spectrum carries out qualitative and quantitative analysis.
The processing of lipstick class sample: accurately take cosmetics sample 0.5g and be placed in 50mL tool plug conical flask, add 20mL methyl alcohol, add again the 0.5mL tetrahydrofuran, put ultrasonic extraction 20min in ultrasonic extractor, said extracted liquid is poured in centrifuge tube with 10000r/min centrifuging 15min, got supernatant, adopt 35 ℃ of nitrogen to blow near and do, be settled to 1mL with 10% methanol aqueous solution, with Oasis HLB solid-phase extraction column, said extracted liquid purified.Adopt the pre-drip washing of 5mL methyl alcohol, the 5mL water balance with 1mL sample loading after above processing, first with 1mL 20% methanol-water drip washing, discards leacheate, then with 3mL80% methanol-water wash-out, collects eluent.Through anhydrous sodium sulfate dehydration, 35 ℃ of nitrogen blow and are concentrated into 1mL, and through membrane filtration, gas chromatography-mass spectrum carries out qualitative and quantitative analysis.
Chromatographic column: HP-Innowax (60m * 0.25mm * 0.50 μ m);
Injector temperature: 200 ℃;
Flow rate of carrier gas: 1.2mL/min (constant current mode), split sampling, split ratio 10: 1;
Temperature programme: 60 ℃ of initial temperatures (keeping 3min) are warming up to 100 ℃ (keeping 2min) with 4 ℃/min, then are warming up to 220 ℃ with 20 ℃/min; Bulk analysis time 21min.
The mass spectrum condition:
Chromatography-mass spectroscopy interface temperature: 250 ℃;
Ion source temperature: 230 ℃;
Ionization mode: EI, the mass scanning scope is (10～100) amu;
Solvent delay: 5min;
Monitoring mode: select ion monitoring (SIM);
Selecting qualitative ion is 53,52,26, and wherein quota ion is 53.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention adopts the ion monitoring method of selecting, selection m/z53 is quota ion, external standard method is quantitative, prepare respectively the vinyl cyanide standard operation liquid of 0.1,0.2,0.5,1.0 and 2.0 μ g/mL, with peak area drawing standard curve, equation of linear regression is y=11004x-168.63, R
2=0.9997, take the interpolation concentration of 3 times of signal to noise ratio (S/N ratio)s as detectability, detect and be limited to 4mg/kg.
The method of the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry of the present invention is measured the cosmetic sample of the cream frost that do not contain vinyl cyanide, aqua, loose powder, shampoo, lipstick, add respectively the recovery and Precision Experiment, add 4,8 and three concentration levels of 80mg/kg (each add concentration replicate determination 6 times) in sample.
Record the recovery between 84.0%～101.0%, precision test records relative standard deviation between 1.1%～4.2%.Above embodiment is described the preferred embodiment of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. the method for the vinyl cyanide in Cosmetics by Gas Chromatography-Mass Spectrometry, comprise the steps:
Add methyl alcohol in the 0.5g testing sample, ultrasonic extraction, extract is centrifugal, get supernatant, nitrogen dries up, with the 10% methanol aqueous solution dissolving of 1ml, then use hydrophilic lipophilic Solid-Phase Extraction column purification, first with the 20% methanol aqueous solution drip washing of 1ml, discard leacheate, again with the percent by volume 80% hydrophilic lipophilic solid-phase extraction column of methanol aqueous solution wash-out of 3ml, collect eluent, the eluent that obtains dewaters, and is concentrated, membrane filtration carries out Gas Chromatography-Mass Spectrometry;
The chromatographic column of gas chromatography is the fixedly chromatographic column of phase of bonding/crosslinked PVOH, and specification is 60 m * 0.25 mm * 0.50 μ m;
The chromatographic column adopting temperature programme: 60 ℃ keep 3 min, and then 4 ℃/min is warming up to 100 ℃ of maintenance 2 min, then is warming up to 220 ℃ with 20 ℃/min;
Split sampling, split ratio are 10:1;
Described cosmetics are cream frost, aqua, loose powder, shampoo or lipstick, when described cosmetics are cream frost, aqua, loose powder or shampoo, add 20 mL methyl alcohol to extract in the 0.5g testing sample; When described cosmetics are lipstick, add 20 mL methyl alcohol and 0.5 mL tetrahydrofuran to extract in the 0.5g testing sample.
2. method according to claim 1, it is characterized in that: described ultrasonic extraction time is 20 min.
3. method according to claim 1, is characterized in that: described centrifugal rotational speed 10000 r/min, centrifuging 15 min.
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| CN102721765B (en) * | 2012-06-27 | 2013-12-04 | 中国科学院宁波材料技术与工程研究所 | Method for determining content of acrylonitrile monomer in polyacrylonitrile polymer liquid |
| CN103048401B (en) * | 2012-12-07 | 2014-04-30 | 中国检验检疫科学研究院 | Determining method for 15 kinds of forbidden nitro imidazoles antibiotics in cosmetics |
| CN114924013A (en) * | 2022-05-12 | 2022-08-19 | 广东铭康香精香料有限公司 | Method for determining various perfume ingredients in cosmetics by gas chromatography-tandem mass spectrometry |
| CN115112804B (en) * | 2022-07-28 | 2023-11-21 | 宜宾五粮液股份有限公司 | Method for detecting sterols in white spirit |
| CN115452988A (en) * | 2022-09-15 | 2022-12-09 | 宣城研一新能源科技有限公司 | Method for detecting acrylonitrile content in wastewater through gas chromatography |
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